Thermoelectric power generation and mineral extraction from brines

ABSTRACT

Disclosed herein is a method and apparatus that uses a brine from a well that is used to both generate electricity and recover valuable minerals present in the brine. The method and apparatus uses a hydrophobic membrane to separate water vapor from the brine to concentrate the brine that is then used to recover the minerals.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 15/138,554, filed Apr. 26, 2016, which claims the benefit of U.S.Provisional Application No. 62/220,676, filed on Sep. 18, 2015, whichare both incorporated herein by reference in their entirety.

GOVERNMENT LICENSE RIGHTS

This invention was made with government support under DE-EE0006746awarded by the Department of Energy (DOE). The government has certainrights in the invention.

BACKGROUND

Geothermal resources provide the opportunity for low-cost renewablebase-load power generation. Today, however, only high-temperatureresources (brines) are able to be harvested economically. The thermalenergy extracted from these high-temperature geothermal reservoirs isconverted to electricity through use of conventional steam or organicRankine power cycles. Systems based on these power cycles are verymature and efficient under high-temperature thermal inputs. However,conversion efficiency decreases substantially as resource temperaturedecreases. As volumetric power densities also decrease at low resourcetemperatures, the decreases in efficiency are accompanied by dramaticincreases in power specific capital costs. Additionally, in small-scaledistributed applications, turbo-machinery based systems experiencefurther decreases in efficiency and increases in power specific capitalcost.

SUMMARY

Disclosed herein is a method for generating electricity and recovering amineral from a brine comprising the steps of:

a) providing a first brine comprising water, silica, one or morepolyvalent ions, and at least one mineral from a well, wherein the firstbrine has a temperature below about 150° C.;

b) removing at least a portion of the silica from the first brine,thereby producing a second brine;

c) removing at least a portion of the water from the second brine bypassing water vapor generated from the second brine through ahydrophobic membrane, thereby producing a third brine, wherein the thirdbrine has a higher concentration of the at least one mineral than thesecond brine;

d) contacting at least a portion of the water vapor that passed throughthe hydrophobic membrane with a thermoelectric module, therebygenerating electricity; and

e) recovering at least a portion of the at least one mineral from thethird brine.

Also disclosed herein is a method for generating electricity andrecovering a mineral from a brine comprising the steps of:

a) providing a first brine comprising water, silica, one or morepolyvalent ions, and at least one mineral from a well, wherein the firstbrine has a temperature below about 300° C.;

b) removing at least a portion of the water from the first brine bypassing water vapor generated from the first brine through a firsthydrophobic membrane, thereby producing a fourth brine, wherein thefourth brine is at least 5% more concentrated in total solids than thefirst brine;

c) contacting at least a portion of the water vapor that passed throughthe first hydrophobic membrane with a thermoelectric module, therebygenerating electricity;

d) removing at least a portion of the silica, one or more polyvalentions from the fourth brine, thereby producing a fifth brine;

e) removing at least a portion of the water from the fifth brine bypassing water vapor generated from the fifth brine through a secondhydrophobic membrane, thereby producing a sixth brine, wherein the sixthbrine has a higher concentration of the at least one mineral than thefifth brine; and

f) recovering at least a portion of the at least one mineral from thesixth brine.

Also disclosed herein is an apparatus comprising a) a housing comprisingfirst inlet and a first outlet, wherein the housing comprises a bottomwall and an opposed top wall, wherein the bottom wall and the top wallare spaced apart relative to a vertical axis, wherein the first inletand the first outlet are spaced apart relative to a longitudinal axis;b) a hydrophobic membrane positioned within the housing, wherein thehydrophobic membrane is positioned between the top wall of the housingand both the first inlet and the first outlet relative to the verticalaxis; and a thermoelectric module positioned within the housing, whereinthe thermoelectric module is positioned between the top wall and thehydrophobic membrane relative to the vertical axis.

Additional advantages of the invention will be set forth in part in thedescription which follows, and in part will be obvious from thedescription, or may be learned by practice of the invention. Theadvantages of the invention will be realized and attained by means ofthe elements and combinations particularly pointed out in the appendedclaims. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are not restrictive of the invention, as claimed.

DETAILED DESCRIPTION OF THE FIGURES

These and other features of the preferred embodiments of the inventionwill become more apparent in the detailed description in which referenceis made to the appended drawings wherein:

FIG. 1 shows a non-limiting schematic of an apparatus disclosed herein.

FIG. 2 shows a non-limiting schematic of an apparatus and methodincluding thermodynamic out- and input disclosed herein.

FIGS. 3A and 3B show a non-limiting scheme of a method disclosed herein.

FIG. 4 shows data from a silica removal procedure.

FIG. 5 shows kinetic data from a silica removal procedure.

FIG. 6 shows data from nanofiltration experiments.

DETAILED DESCRIPTION

The present invention can be understood more readily by reference to thefollowing detailed description, examples, drawings, and claims, andtheir previous and following description. However, before the presentdevices, systems, and/or methods are disclosed and described, it is tobe understood that this invention is not limited to the specificdevices, systems, and/or methods disclosed unless otherwise specified,as such can, of course, vary. It is also to be understood that theterminology used herein is for the purpose of describing particularaspects only and is not intended to be limiting.

The following description of the invention is provided as an enablingteaching of the invention in its best, currently known embodiment. Tothis end, those skilled in the relevant art will recognize andappreciate that many changes can be made to the various aspects of theinvention described herein, while still obtaining the beneficial resultsof the present invention. It will also be apparent that some of thedesired benefits of the present invention can be obtained by selectingsome of the features of the present invention without utilizing otherfeatures. Accordingly, those who work in the art will recognize thatmany modifications and adaptations to the present invention are possibleand can even be desirable in certain circumstances and are a part of thepresent invention. Thus, the following description is provided asillustrative of the principles of the present invention and not inlimitation thereof.

It is also to be understood that the terminology used herein is for thepurpose of describing particular aspects only and is not intended to belimiting. Although any devices and methods similar or equivalent tothose described herein can be used in the practice or testing of thepresent invention, example methods and materials are now described.

As used in the specification and in the claims, the term “comprising”can include the aspects “consisting of” and “consisting essentially of.”Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. In this specification and inthe claims, which follow, reference will be made to a number of termswhich shall be defined herein.

As used in the specification and the appended claims, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a subject” includestwo or more subjects.

As used herein, the terms “about” and “at or about” mean that the amountor value in question can be the value designated some other valueapproximately or about the same. It is generally understood, as usedherein, that it is the nominal value indicated ±10% variation unlessotherwise indicated or inferred. The term is intended to convey thatsimilar values promote equivalent results or effects recited in theclaims. That is, it is understood that amounts, sizes, formulations,parameters, and other quantities and characteristics are not and neednot be exact, but can be approximate and/or larger or smaller, asdesired, reflecting tolerances, conversion factors, rounding off,measurement error and the like, and other factors known to those ofskill in the art.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. When such a range isexpressed, another aspect includes from the one particular value and/orto the other particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another aspect. It will be furtherunderstood that the endpoints of each of the ranges are significant bothin relation to the other endpoint, and independently of the otherendpoint. It is also understood that there are a number of valuesdisclosed herein, and that each value is also herein disclosed as“about” that particular value in addition to the value itself. Forexample, if the value “10” is disclosed, then “about 10” is alsodisclosed. It is also understood that each unit between two particularunits are also disclosed. For example, if 10 and 15 are disclosed, then11, 12, 13, and 14 are also disclosed.

Moreover, it is to be understood that unless otherwise expressly stated,it is in no way intended that any method set forth herein be construedas requiring that its steps be performed in a specific order.Accordingly, where a method claim does not actually recite an order tobe followed by its steps or it is not otherwise specifically stated inthe claims or descriptions that the steps are to be limited to aspecific order, it is no way intended that an order be inferred, in anyrespect. This holds for any possible non-express basis forinterpretation, including: matters of logic with respect to arrangementof steps or operational flow; plain meaning derived from grammaticalorganization or punctuation; and the number or type of aspects describedin the specification.

1. Method and Apparatus

Electricity is currently generated from high-temperature (>˜300° C.)resources, such as, for example high-temperature brines, through use ofthe steam Rankine cycle, and from medium-temperature (>190° C.-300° C.)resources, such as, for example medium-temperature brines, through useof the organic Rankine cycle. However, low-temperature resources (≤190°C.), such as, for example, a low-temperature brine, are generally notused to produce electricity. These brines contain minerals, such as, forexample, lithium, cobalt, nickel, and rare earth elements. It would bedesired to recover these metals.

Accordingly, there is a need in the art for methods and apparatuses thatcan utilize a low-temperature brine to generate electricity and torecover metal found in the brines. Such a method and apparatus aredisclosed herein.

Disclosed herein are methods and apparatuses that can utilizemedium-temperature and low-temperature brines to produce electricity.Furthermore, the methods and apparatuses disclosed herein can be used toalso recover minerals from these medium-temperature and low-temperaturebrines.

In circumstances where low-temperature resources are used for powergeneration, binary organic Rankine cycles are conventionally used.However, such a system experience low conversion efficiencies and highpower specific capital costs. Furthermore, the efficiency and specificcapital costs of all of these turbo-machinery based conversion systemsare highly sensitive to scale. As such, these systems have challengesbeing economically feasible in small distributed generationapplications.

The economics of stand-alone high-value mineral extraction fromgeothermal brine processes are not attractive when the minerals are inlow concentrations, as large volumes of brine are needed to be processedto extract minimum amounts of mineral. There is also a minimum totalresource size that is needed to justify commercial extraction.

While neither power generation from medium-temperature andlow-temperature brines, nor dilute mineral extraction systems orapparatuses are economically feasible on their own, it has been foundherein that a combined process that leverages the strengths of each canbe implemented to synergistically create an economically competitivesystem. Such an apparatus and method are described herein.

The apparatus and method described herein using one, or alternativelytwo, thermally driven membrane distillation component(s) to extractwater vapor from a medium temperature and/or low-temperature brine toproduce electrical power via a solid-state thermoelectric generator(s),while simultaneously concentrating the medium temperature and/orlow-temperature brine to facilitate a brine suitable for high-valuemineral extraction.

Two thermally driven membrane distillation component(s) are typicallyused with medium-temperature brines. The first thermally driven membranedistillation component(s) typically comprises a ceramic hydrophobicmembrane that can withstand the temperature of the medium-temperaturebrine, for example, temperatures above about 190° C. The secondthermally driven membrane distillation component(s) typically comprisesa polymeric hydrophobic membrane that can efficiently separate watervapor from a liquid water and minerals, such as, for example, lithium.The polymeric hydrophobic membrane can be used for brines with a lowertemperature, for example, temperatures below about 190° C. or belowabout 150° C.

The combination of power generation and mineral extraction disclosedherein can make an otherwise uneconomical process economically feasible.

The apparatus and method disclosed herein generally comprises alow-value inhibitory mineral precipitation and separation process,followed by a thermally driven membrane separation technology, whichprovides for the thermoelectric power generation and concentration ofthe brine that is used for the high-value mineral extraction.

Disclosed herein is a first method for generating electricity andrecovering a mineral from a brine comprising the steps of:

a) providing a first brine comprising water, silica, one or morepolyvalent ions, and at least one mineral from a well, wherein the firstbrine has a temperature below about 300° C.;

b) removing at least a portion of the silica from the first brine,thereby producing a second brine;

c) removing at least a portion of the water from the second brine bypassing water vapor generated from the second brine through ahydrophobic membrane, thereby producing a third brine, wherein the thirdbrine has a higher concentration of the at least one mineral than thesecond brine;

d) contacting at least a portion of the water vapor that passed throughthe hydrophobic membrane with a thermoelectric module, therebygenerating electricity; and

e) recovering at least a portion of the at least one mineral from thethird brine.

Also disclosed herein is a second method for generating electricity andrecovering a mineral from a brine comprising the steps of:

a) providing a first brine comprising water, silica, one or morepolyvalent ions, and at least one mineral from a well, wherein the firstbrine has a temperature below about 300° C.;

b) removing at least a portion of the water from the first brine bypassing water vapor generated from the first brine through a firsthydrophobic membrane, thereby producing a fourth brine, wherein thefourth brine is at least 5% more concentrated in total solids than thefirst brine;

c) contacting at least a portion of the water vapor that passed throughthe first hydrophobic membrane with a thermoelectric module, therebygenerating electricity;

d) removing at least a portion of the silica, one or more polyvalentions from the fourth brine, thereby producing a fifth brine;

e) removing at least a portion of the water from the fifth brine bypassing water vapor generated from the fifth brine through a secondhydrophobic membrane, thereby producing a sixth brine, wherein the sixthbrine has a higher concentration of the at least one mineral than thefifth brine; and

f) recovering at least a portion of the at least one mineral from thesixth brine.

In one aspect, the second method further comprises contacting at least aportion of the water vapor that was generated from the fifth brine andpassing it through the second hydrophobic membrane with a thermoelectricmodule, thereby generating electricity.

The steps in the two methods disclosed correspond as follows: 1. step a)in the first method corresponds to step a) in the second method; 2. stepb) in the first method corresponds to step d) in the second method; 3.step c) in the first method corresponds to step e) in the second method;4. Step e) in the first method corresponds to step f) in the secondmethod.

The method disclosed herein can be performed by the apparatus disclosedherein. With reference to FIG. 1, disclosed herein is an apparatus 100comprising a) a housing 102 comprising first inlet 104 and a firstoutlet 105, wherein the housing 102 comprises a bottom wall 106 and anopposed top wall 108, wherein the bottom wall 106 and the top wall 108are spaced apart relative to a vertical axis 110, wherein the firstinlet 104 and the first outlet 105 are spaced apart relative to alongitudinal axis 112; b) a hydrophobic membrane 114 positioned withinthe housing 102, wherein the hydrophobic membrane 114 is positionedbetween the top wall 108 of the housing 102 and both the first inlet 104and the first outlet 105 relative to the vertical axis 110; and athermoelectric module 116 positioned within the housing 102, wherein thethermoelectric module 116 is positioned between the top wall 108 and thehydrophobic membrane 114 relative to the vertical axis 110.

The non-limiting process flow of a method and the thermodynamic inputand output disclosed herein is shown FIGS. 2 and 3. FIGS. 1, 2, and 3shows the same process flow of a method disclosed herein in varyingdetail.

In one aspect, the housing 102 further comprises a second outlet 118positioned between the hydrophobic membrane 114 and the thermoelectricmodule 116 relative to the vertical axis 110.

In one aspect, the housing 102 further comprises a third inlet 120 and athird outlet 122 positioned between the upper wall 108 and thethermoelectric module 116 relative to the vertical axis 110, wherein thehousing 102 is configured to transport a coolant into the housing 102from the third inlet 120 and out from the housing 102 via the thirdoutlet 122.

In one aspect, the housing 102 is configured to transport brine into thehousing 102 from the first inlet 104 and brine out of the housing 102from the first outlet 105.

In one aspect, the housing 102 is in communication with a silica removalunit 128 via the first inlet 104. In another aspect, the housing 102 isin communication with a polyvalent ion removal unit 124 via the firstinlet 104. The polyvalent ion removal unit 124 can comprise anano-filtration membrane. The arrangement of the silica removal unit 128and the polyvalent ion removal unit 124 can vary relative to the housing102. In one aspect, the silica removal unit 128 is in communication withthe polyvalent ion removal unit 124, which is in communication with thehousing 102 via the first inlet 104. In another aspect, the polyvalention removal unit 124 is in communication with the silica removal unit128, which is in communication with the housing 102 via the first inlet104.

In one aspect, in an apparatus that performs the second method, thesilica removal unit is in further communication with an second apparatus(not shown in FIG. 1) comprising a) a housing 102 comprising first inlet104 and a first outlet 105, wherein the housing 102 comprises a bottomwall 106 and an opposed top wall 108, wherein the bottom wall 106 andthe top wall 108 are spaced apart relative to a vertical axis 110,wherein the first inlet 104 and the first outlet 105 are spaced apartrelative to a longitudinal axis 112; b) a hydrophobic membrane 114positioned within the housing 102, wherein the hydrophobic membrane 114is positioned between the top wall 108 of the housing 102 and both thefirst inlet 104 and the first outlet 105 relative to the vertical axis110; and a thermoelectric module 116 positioned within the housing 102,wherein the thermoelectric module 116 is positioned between the top wall108 and the hydrophobic membrane 114 relative to the vertical axis 110.In this aspect, the apparatus comprises two different housings etc.,which is shown in FIG. 3B. In the second apparatus 100, the hydrophobicmembrane 114 can be a ceramic hydrophobic membrane. In thisconfiguration, the first brine can be a medium-temperature brine. Thetemperature of the first brine is lowered by passing water vaporgenerated from the first brine through a first hydrophobic membrane,thereby producing a fourth brine, wherein the fourth brine is at leastabout 5% more concentrated in total solids than the first brine. Thefourth brine can have a temperature of below about 190° C. or belowabout 150° C. The fourth brine then enters the silica removal unit 128and in turn the polyvalent ion removal unit 124 to produce a fifthbrine. The fifth brine then enters the first housing 102 (shown inFIG. 1) to separate water vapor from the fifth brine to produce thesixth brine. At least a portion of the one or more minerals is recoveredfrom the sixth brine.

In one aspect, the fourth brine is at least about 10% more concentratedin total solids than the first brine. For example, the fourth brine canbe from about 10% to about 15% more concentrated in total solids thanthe first brine. Total solids in the first brine include, but are notlimited to silica and minerals, or a combination thereof.

In one aspect, when step b) or d), depending on the first or secondmethod, removes at least a portion of the silica from the first orfourth brine, thereby producing a second or fifth brine that cancomprise precipitating silicates from the first or fourth brine and/orfiltering the first or fourth brine. For example, removing at least aportion of the silica from the first or fourth brine, thereby producinga second or fifth brine can comprise precipitating silicates from thefirst or fourth brine. In another example, removing at least a portionof the silica from the first brine, thereby producing a second or fifthbrine can comprise precipitating and filtering silicates from the firstor fourth brine. The second or fifth brine has a lower content of silicathan the first brine. In one aspect, the second brine has a silicaconcentration of less than 0.01 wt %, such as, for example, a silicaconcentration of less than 0.001 wt %. In one aspect, at least 80 wt %,85 wt %, or 90 wt % of the silica is removed from the first brine. Inanother aspect, at least 80 wt %, 85 wt %, or 90 wt % of the silica isremoved from the second brine. The silica removal unit 128 is a unitthat is configured to remove silica from a brine, such as, the firstbrine, second brine, or fourth brine. The silica can be removed from thefirst or fourth brine by precipitating silicates from the first orfourth brine in the silica removal unit 128. The silica removal unit 128can use addition of a caustic material to increase the pH to, forexample, about 9, of the brine to precipitate the silica in to the solidphase. In addition, ferric chloride may be added to enhance silicaremoval. The first bring can subsequently be mechanically filtered toremove additional silica.

In one aspect, the method further comprises adjusting the pH of thefirst brine to a pH from about 5.0 to about 7.0, such as, for example, apH from about 5.5 to about 6.5, such as, for example, a pH of about 6.0.

In one aspect, the method further comprises before step c) or in stepd), depending on the first or second method, a step comprising removingat least a portion of the one or more polyvalent ions present in thefirst brine, second brine, or fourth brine. For example, the method canfurther comprise before step c) a step comprising removing at least aportion of the one or more polyvalent ions present in the first brine.In another example, the method a step d) comprising removing at least aportion of the one or more polyvalent ions present in the fourth brine.In another aspect, the method can further comprise before step c) a stepcomprising removing at least a portion of the one or more polyvalentions present in the second brine. The one or more polyvalent ions cancomprise Co²⁺, Ni²⁺, or polyvalent rare earth elements, or a combinationthereof. The polyvalent ion removal unit 124 can comprise anano-filtration membrane, which is configured to remove polyvalent ionsfrom a brine, such as, the first brine, second brine, or fourth brine.As such, the step of removing at least a portion of the one or morepolyvalent ions present in the first brine, second brine, or fourthbrine can comprise filtering the first, second, or fourth brine througha nano-filtration membrane. Nano-filtration is known in the art and is amembrane filtration-based method that uses nanometer sized pores,generally having pore sizes from 1-10 nanometers. Nano-filtrationmembranes can be made from polymer thin films, such as, for example,polyethylene terephthalate. The one or more polyvalent ions can compriseCa²⁺ and Mg²⁺. In one aspect, at least 85 wt %, 90 wt %, or 95 wt % ofthe one or more polyvalent ions in the first brine is removed. Inanother aspect, at least 85 wt %, 90 wt %, or 95 wt % of the one or morepolyvalent ions in the second brine is removed. In another aspect, atleast 85 wt %, 90 wt %, or 95 wt % of the one or more polyvalent ions inthe fourth brine is removed. The precipitation and separation of silicaand the one or more polyvalent ions removes components that can causescaling and/or fouling in the hydrophobic membrane/apparatus andinterfere with the downstream high-value mineral extraction process.

In one aspect, the method can further comprise recovering at least aportion of the polyvalent ion from the second or fourth brine, whereinthe polyvalent ion comprises Co²⁺ or Ni²⁺, or a combination thereof. Therecovering of the polyvalent ion can comprise mixing an ionic liquidwith the second or fourth brine.

In one aspect, the first brine has a temperature below about 300° C. Inone aspect, the first brine has a temperature below or equal to about190° C. In another aspect, the first brine has a temperature below orequal to about 180° C. In yet another aspect, the first brine has atemperature below or equal to about 170° C. In yet another aspect, thefirst brine has a temperature below or equal to about 160° C. In yetanother aspect, the first brine has a temperature below or equal about150° C. In yet another aspect, the first brine has a temperature fromabout 90° C. to about 190° C. In yet another aspect, the first brine hasa temperature from about 90° C. to about 150° C. In yet another aspect,the first brine has a temperature from about 150° C. to about 190° C.

The second or fifth brine enters the apparatus 100 via the first inlet104. The first, second, and fifth brine can be a low-temperature brine,with a temperature below or equal to about 190° C. or below or equal toabout 150° C. The first, second, and fifth brine can be alow-temperature brine, with a temperature below from about 90° C. toabout 190° C. or about 90° C. to about 150° C. The first brine canoriginate from a variety of geothermal or waste water sources. Forexample, first brine can originate from a low-temperature reservoirfound in the vicinity of a tectonic plate line. The location of tectonicplate lines are known to those skilled in the art. Tectonic plate linescan be found, in for example, southern California, Nevada, Chile,Bolivia, China, Tibet, Eastern Africa, and Afghanistan.

The first brine comprises water, silica, one or more polyvalent ions,and at least one mineral. The first brine can comprise less than about 5wt % of solids, such as, less than about 5 wt % of silica, one or morepolyvalent ions, and at least one mineral. In one aspect, the firstbrine comprises less than 0.1 wt % of the at least one mineral. Inanother aspect, the first brine can comprise from about 0.01 wt % toabout 0.1 wt % of the al least one mineral. The first brine can furthercomprise rare earth elements, such as, one or more of the fifteenlanthanides in the periodic table, as well as scandium and yttrium.

In one aspect, the at least one mineral comprises lithium, zinc,magnesium, cobalt, nickel, or uranium, or a combination thereof. Forexample, the at least one mineral can comprise lithium. In anotherexample, the at least one mineral can comprise zinc. In yet anotherexample, at least one mineral can comprise magnesium. In yet anotherexample, at least one mineral can comprise uranium. In yet anotherexample, at least one mineral can comprise a combination of lithium,zinc, magnesium, and uranium. In yet another example, at least onemineral can comprise cobalt or nickel, or a combination thereof.

In one aspect, the first brine comprises less than 0.1 wt % of lithium,zinc, magnesium, or uranium, or a combination thereof. For example, thefirst brine can comprise less than 0.1 wt % of lithium. In yet anotherexample, the first brine can comprise from about 0.01 wt % to about 0.1wt % of lithium.

The first brine exits the well under pressure. In one aspect, the firstbrine is under a pressure from about 1 bar to about 5 bar, such as, forexample a pressure from about 3 bar to about 5 bar.

The hydrophobic membrane 114 allows water vapor to pass through, whilerejecting liquid water and dissolved solids such as, for example, the atleast one mineral or the one or more polyvalent ions, or a combinationthereof. In one aspect, the hydrophobic membrane is a ceramichydrophobic membrane, which has ceramic hollow microfibers. Ceramichydrophobic membranes are resistant to high temperatures and, thus, aresuitable to use with brines, such as a first brine, at temperaturesabove about 150° C., above about 175° C., or above about 200° C. Ceramichydrophobic membranes are used to produce a fourth brine from a firstbrine, wherein the fourth brine is at least 5% more concentrated intotal solids than the first brine. In one aspect, the fourth brine isfrom about 10% to about 20% more concentrated in total solids than thefirst brine.

In another aspect, the hydrophobic membrane is a polymeric hydrophobicmembrane. Polymeric hydrophobic membranes are not as temperatureresistant as a ceramic hydrophobic membrane. However, the polymerichydrophobic membrane has smaller pores than the ceramic hydrophobicmembrane, which allows for a higher degree of separation of water vaporand solids. Thus, a polymeric hydrophobic membrane is suitable withbrines, such as a second or fifth brine, at temperatures below about150° C. In such an example when the second brine has a temperature belowabout 150° C.

The temperature and pressure of the second or fifth brine allows for asignificant amount of water vapor to be generated, which passes throughthe hydrophobic membrane 114. Extraction of water vapor from liquidwater streams through use of hydrophobic membranes in thermally drivenmembrane distillation is well known in the art. The polymerichydrophobic membrane can be constructed of polyvinylidene fluoride(PVDF). Suitable hydrophobic membranes are commercially available. Themineral content of the third brine is higher than in the second brine.Similarly the mineral content of the sixth brine is higher than in thefifth brine. In one aspect, the concentration of the at least onemineral in the third or sixth brine is from about 0.01 wt % to about 0.5wt %. In another aspect, the concentration of the at least one mineralin the third or sixth brine is from about 0.02 wt % to about 0.3 wt %.The increase in concentration of minerals in the third or sixth brineenhances the activity, and minimizes the amount of sorbent needed, ofsorption-based high-value mineral extraction processes.

The water vapor that has passed through the hydrophobic membrane 114 hasa lower temperature as compared to the temperature of the second brine.For example, the temperature for the water vapor can be up to about 40°C. lower as compared to the second or fifth brine, such as from about 5°C. to about 40° C. lower as compared to the second or fifth brine. Thewater vapor then contacts the thermoelectric module 116. The water vaporcondenses on the thermoelectric module 116 and latent heat istransferred from the water vapor to the thermoelectric module 116. Thethermoelectric module 116 is configured to operate with a hot side of ata temperature from about 100° C. to about 180° C., and a cool side ofabout 10° C. to about 80° C. In another example, the thermoelectricmodule 116 is configured to operate with a hot side of at a temperaturefrom about 120° C. to about 180° C., and a cool side of about 10° C. toabout 30° C. The cool side of the thermoelectric module 116 is incontact with the coolant that enters the housing 102 via the third inlet120 and exits the housing 102 via the third outlet 122. As such, thethermoelectric module 116 can be configured to operate at a temperaturedifference from about 80° C. to about 150° C. For example, thethermoelectric module 116 can be configured to operate at a temperaturedifference from about 80° C. to about 120° C. In another example, thethermoelectric module 116 can be configured to operate at a temperaturedifference from about 90° C. to about 130° C.

The hot side of the thermoelectric module 116 can be tailored to have asurface texture or module orientation that encourages condensation ofthe water vapor and gravity removal of the condensate from the surface,thereby removing any thermal barrier to heat transfer (latent heat) fromthe water vapor and promote heat flow thorough the thermoelectric module116. The thermoelectric module 116 can be of any type or design. Thethermoelectric module 116 can comprise one or more individualthermoelectric module generators, such as, for example, from 1 to 300thermoelectric module generators, or from 1 to 50,000. Electricity isgenerated when heat is transferred from the hot side to the cool side ofthe thermoelectric module 116.

In one aspect, the electrical power density can be from about 1 W/cm² toabout 8 W/cm², such as, for example from 3 W/cm² to about 5 W/cm². Inone aspect, the method generates from about 100 kW to about 50 MW ofelectricity. The size of the apparatus can determine the electricityoutput of the method. The thermoelectric module 116 can comprise p- andn-type thermoelectric couples at a desired size. For example, the sizecan be from 1.0 mm to about 2.0 mm tall and from 1.0 mm to 3 mm squarein the side dimension.

The third or sixth brine exits the housing 102 via the first outlet 105and enters a mineral recovery unit 126. Recovery of minerals, such as,for example, lithium is known in the art. The higher the concentrationof minerals in the third or sixth brine the higher efficiency theapparatus 100 will have. Lithium can be recovered by producing lithiumcarbonate in the mineral recovery unit 126. Furthermore, lithiumrecovery from a brine is, for example, described in U.S. Pat. No.8,753,594 to Burba et al., which is hereby incorporated by reference inits entirety, specifically for its disclosure of lithium recover from abrine. Other suitable lithium recovery processes utilizes aspinel-lithiated manganese oxide sorbent.

In one aspect, the method further comprises injecting the third or sixthbrine after the removal of the at least one mineral in to the well wherethe first brine originated from. The reinjection of the third or sixthbrine into the well allows for the well to maintain its pressure andintegrity for further production of the first brine. In one aspect, therelatively pure water reclaimed after the mineral recover can be used tomeet local water demands (irrigation, potable water, etc.).

The apparatus disclosed herein can be made to a desired scale. Forexample, an industrial size apparatus is disclosed to meet high demandsof large well. In another example, a smaller than industrial apparatusis disclosed to meet demands from a smaller well.

Furthermore, every component in this described system is highly modular.While conventional turbo-machinery based systems and apparatuses requirelarge scale to achieve acceptable efficiencies and specific costs, thedescribed system can be deployed at virtually any scale. This alignswell with the large scale range of potential mineral reserves, allowingfor the power generation system to be sized to the local resource andlocal demand.

2. Aspects

In view of the described apparatus and methods and variations thereof,herein below are described certain more particularly described aspectsof the inventions. These particularly recited aspects should not howeverbe interpreted to have any limiting effect on any different claimscontaining different or more general teachings described herein, or thatthe “particular” aspects are somehow limited in some way other than theinherent meanings of the language and formulas literally used therein.

Aspect 1: A method for generating electricity and recovering a mineralfrom a brine comprising the steps of:

-   -   a) providing a first brine comprising water, silica, one or more        polyvalent ions, and at least one mineral from a well, wherein        the first brine has a temperature below about 300° C.;    -   b) removing at least a portion of the silica from the first        brine, thereby producing a second brine;    -   c) removing at least a portion of the water from the second        brine by passing water vapor generated from the second brine        through a hydrophobic membrane, thereby producing a third brine,        wherein the third brine has a higher concentration of the at        least one mineral than the second brine;    -   d) contacting at least a portion of the water vapor that passed        through the hydrophobic membrane with a thermoelectric module,        thereby generating electricity; and    -   e) recovering at least a portion of the at least one mineral        from the third brine.

Aspect 2: The method of aspect 1, wherein the at least one mineralcomprises lithium, zinc, magnesium, or uranium, or a combinationthereof.

Aspect 3: The method of aspect 1, wherein the at least one mineralcomprises lithium.

Aspect 4: The method of any one of aspects 1-3, wherein theconcentration of the at least one mineral in the first brine is lessthan 0.1 wt %.

Aspect 5: The method of any one of aspects 1-4, wherein the first brineis under a pressure from about 1 bar to about 5 bar.

Aspect 6: The method of any one of aspects 1-4, wherein the first brineis under a pressure from about 3 bar to about 5 bar.

Aspect 7: The method of any one of aspects 1-6, wherein the temperatureof the first brine is from about 90° C. to about 190° C.

Aspect 8: The method of any one of aspects 1-7, wherein removing atleast a portion of the silica from the first brine comprisesprecipitating silicates from the first brine and filtering the firstbrine.

Aspect 9: The method of any one of aspects 1-8, wherein the second brinehas a silica concentration of less than 0.01 wt %.

Aspect 10: The method of any one of aspects 1-9, wherein removing the atleast a portion of the water from the second brine by passing watervapor generated comprises lowering the pressure of the second brine.

Aspect 11: The method of any one of aspects 1-10, wherein the methodfurther comprises before step c) a step comprising removing at least aportion of the one or more polyvalent ions present in the first brine.

Aspect 12: The method of any one of aspects 1-11, wherein liquid wateror solids are not passed through the hydrophobic membrane.

Aspect 13: The method of any one of aspects 1-12, wherein theconcentration of the at least one mineral in the third brine is fromabout 0.01 wt % to about 0.5 wt %.

Aspect 14: The method of any one of aspects 1-12, wherein theconcentration of the at least one mineral in the third brine is fromabout 0.02 wt % to about 0.3 wt %.

Aspect 15: The method of any one of aspects 1-14, wherein thethermoelectric module is configured to operate with a hot side of at atemperature from about 100° C. to about 180° C., and a cool side ofabout 10° C. to about 80° C.

Aspect 16: The method of any one of aspects 1-15, wherein recovering atleast a portion of the at least one mineral from the third brinecomprises extracting the at least one mineral from the third brine.

Aspect 17: The method of any one of aspects 1-16, wherein the methodfurther comprises injecting the third brine after the removal of the atleast one mineral in to the well where the first brine originated from.

Aspect 18: The method of any one of aspects 1-17, wherein the methodgenerates from about 100 kW to about 50 MW of electricity.

Aspect 19: An apparatus comprising:

-   -   a) a housing comprising a first inlet and a first outlet,        wherein the housing comprises a bottom wall and an opposed top        wall, wherein the bottom wall and the top wall are spaced apart        relative to a vertical axis, wherein the first inlet and the        first outlet are spaced apart relative to a longitudinal axis;    -   b) a hydrophobic membrane positioned within the housing, wherein        the hydrophobic membrane is positioned between the top wall of        the housing and both the first inlet and the first outlet        relative to the vertical axis; and    -   c) a thermoelectric module positioned within the housing,        wherein the thermoelectric module is positioned between the top        wall and the hydrophobic membrane relative to the vertical axis.

Aspect 20: The apparatus of aspect 19, wherein the housing furthercomprises a second outlet positioned between the hydrophobic membraneand the thermoelectric module relative to the vertical axis.

Aspect 21: The apparatus of aspects 19 or 20, wherein the housingfurther comprises a third inlet and a third outlet positioned betweenthe upper wall and the thermoelectric module relative to the verticalaxis, wherein the housing is configured to transport a coolant into thehousing from the third inlet and out from the housing via the thirdoutlet.

Aspect 22: The apparatus of any one of aspects 19-21, wherein thehousing is configured to transport brine into the housing from the firstinlet and brine out of the housing from the first outlet.

Aspect 23: The apparatus of any one of aspects 19-22, wherein thehousing is in communication with a silica removal unit via the firstinlet.

Aspect 24: The apparatus of any one of aspects 19-23, wherein thehousing is in communication with a mineral recovery unit via the firstoutlet.

Aspect 25: The apparatus of any one of aspects 19-24, wherein thehousing is in communication with a polyvalent ion removal unit via thefirst inlet.

Aspect 26: The apparatus of any one of aspects 23-25, wherein the silicaremoval unit is in further communication with an second apparatuscomprising:

-   -   a) a housing comprising a first inlet and a first outlet,        wherein the housing comprises a bottom wall and an opposed top        wall, wherein the bottom wall and the top wall are spaced apart        relative to a vertical axis, wherein the first inlet and the        first outlet are spaced apart relative to a longitudinal axis;    -   b) a hydrophobic membrane positioned within the housing, wherein        the hydrophobic membrane is positioned between the top wall of        the housing and both the first inlet and the first outlet        relative to the vertical axis; and    -   c) a thermoelectric module positioned within the housing,        wherein the thermoelectric module is positioned between the top        wall and the hydrophobic membrane relative to the vertical axis.

Aspect 27: The apparatus of any one of aspects 19-26, wherein theapparatus is of industrial size.

Aspect 28: A method for generating electricity and recovering a mineralfrom a brine comprising the steps of:

-   -   a) providing a first brine comprising water, silica, one or more        polyvalent ions, and at least one mineral from a well, wherein        the first brine has a temperature below about 300° C.;    -   b) removing at least a portion of the water from the first brine        by passing water vapor generated from the first brine through a        first hydrophobic membrane, thereby producing a fourth brine,        wherein the fourth brine is at least about 5% more concentrated        in total solids than the first brine;    -   c) contacting at least a portion of the water vapor that passed        through the first hydrophobic membrane with a thermoelectric        module, thereby generating electricity;    -   d) removing at least a portion of the silica and removing at        least a portion of the one or more polyvalent ions from the        fourth brine, thereby producing a fifth brine;    -   e) removing at least a portion of the water from the fifth brine        by passing water vapor generated from the fifth brine through a        second hydrophobic membrane, thereby producing a sixth brine,        wherein the sixth brine has a higher concentration of the at        least one mineral than the fifth brine; and    -   f) recovering at least a portion of the at least one mineral        from the sixth brine.

Aspect 29: The method of aspect 28, wherein the method further comprisescontacting at least a portion of the water vapor that was generated fromthe fifth brine and passed through the second hydrophobic membrane witha thermoelectric module, thereby generating electricity.

Aspect 30: The method of aspects 28 or 29, wherein the first brine has atemperature below about 190° C.

Aspect 31: The method of aspects 28 or 29, wherein the second brine hasa temperature below 150° C. in step d).

Aspect 32: The method of any one of aspects 28-31, wherein the firsthydrophobic membrane is a ceramic hydrophobic membrane.

Aspect 33: The method of any one of aspects 28-32, wherein the secondhydrophobic membrane is a polymeric hydrophobic membrane.

Aspect 34: The method of any one of aspects 28-33, wherein the fourthbrine is from about 10% to about 20% more concentrated in total solidsthan the first brine.

Aspect 35: The method of any one of aspects 28-34, wherein the methodfurther comprises recovering at least a portion of the one or morepolyvalent ions that has been removed from the fourth brine, wherein theone or more polyvalent ions comprises Co²⁺, Ni²⁺, or a polyvalent rareearth metal, or a combination thereof.

Aspect 36: The method of any one of aspects 28-35, wherein the at leastone mineral comprises lithium.

3. Examples

A. Prophetic-Conceptual Design of Apparatus and Method

As described above, a non-limiting process described herein is shown inFIGS. 2, 3A, and 3B. FIG. 2 shows the thermodynamic and process flowmodel for the apparatus disclosed herein. The method precipitates silicawith a removal rate of greater than 80 wt %. Once silica is removednanofiltration (NF) removes polyvalent ions, such as Ca²⁺ and Mg²⁺, bygreater than 85 wt %. The brine is than exposed to a hydrophobicmembrane which separates a portion of the water in the brine to increasethe total dissolved solids in the brine. The hydrophobic membrane allowsfor water vapor to permeate, however no liquid water or dissolved solidswill permeate. Water vapor permeating the membrane condenses on contactwith the colder thermoelectric module, which harnesses the latent heatgiven off by the water vapor to produce electricity and reject wasteheat to an evaporative chilled cooling loop. As water vapor permeatesthe membrane, the remaining brine is concentrated allowing for highactivity and selectivity of the lithium absorption process. In themineral recovery system, a manganese oxide sorbent is utilized toextract lithium from the mineral rich concentrated geothermal brineeffluent, which is then regenerated to produce stable lithium carbonate.Greater than 30 wt % of the overall brine composition, lithiumabsorption in which the sorbent capacity is greater than 40 mg lithium/gsorbent can be used to separate lithium from the brine, and thethermoelectric conversion can have an efficiency of greater than 5.5%(such as from 5.5% to about 10.0%) at using a thermoelectric moduleoperating with a temperature gradient of about 100° C.

The composition of the brines through the apparatus shown in FIG. 2 isprovided in Table 1. The data was generated by using rigorousthermodynamic and process flow modeling software.

TABLE 1 1 1A 1B 1C 1D 2 2A 2B 2C 2D Mole Flow kmol/hr 0 0 0 0 0 0 0 0 00 WATER 140.369 0 140.369 0 140.369 7.01843 0 7.01843 7.01843 0 CA++0.00129 0 0.00129 0.0011 0.00019 0.00019 0 0.00019 0.00019 0 MG++0.02613 0 0.02613 0.02221 0.00392 0.00392 0 0.00392 0.00392 0 NA+0.84181 0 0.84181 0 0.84181 0.84181 0 0.84181 0.84181 0 CL− 0.88521 00.88521 0 0.88521 0.88521 0 0.88521 0.88521 0 S04−− 0.01114 0 0.01114 00.01114 0.01114 0 0.01114 0.01114 0 SI4+ 0.00788 0.00709 0.00079 00.00079 0.00079 0 0.00079 0.00079 0 LI+ 0.01083 0 0.01083 0 0.010830.01083 0 0 0 0 C02 0 0 0 0 0 0 0.05 0.04459 0.04459 0 02 0 0 0 0 0 00.05 0.04729 0.04729 0 LI2C03 0 0 0 0 0 0 0 0.00541 0 0.00541 Mass Flowkg/hr 0 0 0 0 0 0 0 0 0 0 WATER 2528.78 0 2528.78 0 2528.78 126.439 0126.439 126.439 0 CA++ 0.05186 0 0.05186 0.04408 0.00778 0.00778 00.00778 0.00778 0 MG++ 0.63507 0 0.63507 0.53981 0.09526 0.09526 00.09526 0.09526 0 NA+ 19.3526 0 19.3526 0 19.3526 19.3526 0 19.352619.3526 0 CL− 31.3837 0 31.3837 0 31.3837 31.3837 0 31.3837 31.3837 0S04−− 1.06991 0 1.06991 0 1.06991 1.06991 0 1.06991 1.06991 0 SI4+0.22127 0.19914 0.02213 0 0.02213 0.02213 0 0.02213 0.02213 0 LI+0.07515 0 0.07515 0 0.07515 0.07515 0 0 0 0 C02 0 0 0 0 0 0 2.200491.96223 1.96223 0 02 0 0 0 0 0 0 1.59994 1.51332 1.51332 0 LI2C03 0 0 00 0 0 0 0.40003 0 0.40003 Mass Frac 0 0 0 0 0 0 0 0 0 0 WATER 0.97955 00.97963 0 0.97985 0.70856 0 0.69378 0.69531 0 CA++   2E−05 0   2E−050.07549   3E−06 4.4E−05 0 4.3E−05 4.3E−05 0 MG++ 0.00025 0 0.000250.92451 3.7E−05 0.00053 0 0.00052 0.00052 0 NA+ 0.0075 0 0.0075 0 0.00750.10845 0 0.10619 0.10642 0 CL− 0.01216 0 0.01216 0 0.01216 0.17587 00.17221 0.17258 0 S04− 0.00041 0 0.00041 0 0.00041 0.006 0 0.005870.00588 0 SI4+ 8.6E−05 1 8.6E−06 0 8.6E−06 0.00012 0 0.00012 0.00012 0LI+ 2.9E−05 0 2.9E−05 0 2.9E−05 0.00042 0 0 0 0 C02 0 0 0 0 0 0 0.579010.01077 0.01079 0 02 0 0 0 0 0 0 0.42099 0.0083 0.00832 0 LI2C03 0 0 0 00 0 0 0.00219 0 1 Total Flow kmol/hr 142.153 0.00709 142.146 0.02331142.122 8.77232 0.1 8.85878 8.85337 0.00541 Total Flow kg/hr 2581.570.19914 2581.37 0.58389 2580.79 178.445 3.80043 182.246 181.846 0.40003Temperature C. 150 150 150 150 150 150 20 20 20 20 Pressure bar 4.750894.75089 4.75089 4.75089 4.75089 4.75089 1 1 1 1 Vapor Frac 0 0 0 0 0 0 10.00628 0.00629 0 Liquid Frac 0.98745 0 0.9875 0 0.98766 0.80007 00.79696 0.79683 1 Density kg/cum 866.973 2326.17 866.931 927.192 866.918920.536 1.55925 119 118.756 564.903 3 4 5 9 10 10A 11 12 13 Mole Flowkmol/hr 0 0 0 0 0 0 0 0 0 WATER 133.35 133.35 56.0071 6769.79 6769.796769.79 6769.79 77.3431 77.3431 CA++ 0 0 0 0 0 0 0 0 0 MG++ 0 0 0 0 0 00 0 0 NA+ 0 0 0 0 0 0 0 0 0 CL− 0 0 0 0 0 0 0 0 0 S04−− 0 0 0 0 0 0 0 00 SI4+ 0 0 0 0 0 0 0 0 0 LI+ 0 0 0 0 0 0 0 0 0 C02 0 0 0 0 0 0 0 0 0 020 0 0 0 0 0 0 0 D LI2C03 0 0 0 0 0 0 0 0 0 Mass Flow kg/hr 0 0 0 0 0 0 00 0 WATER 2402.34 2402.34 1008.98 121960 121960 121960 121960 1393.361393.36 CA++ 0 0 0 0 0 0 0 0 0 MG++ 0 0 0 0 0 0 0 0 0 NA+ 0 0 0 0 0 0 00 0 CL− 0 0 0 0 0 0 0 0 0 S04−− 0 0 0 0 0 0 0 0 0 SI4+ 0 0 0 0 0 0 0 0 0LI+ 0 0 0 0 0 0 0 0 0 C02 0 0 0 0 0 0 0 0 0 02 0 0 0 0 0 0 0 0 0 LI2C030 0 0 0 0 0 0 0 0 Mass Frac 0 0 0 0 0 0 0 0 0 WATER 1 1 1 1 1 1 1 1 1CA++ 0 0 0 0 0 0 0 0 0 MG++ 0 0 0 0 0 0 0 0 0 NA+ 0 0 0 0 0 0 0 0 0 CL−0 0 0 0 0 0 0 0 0 S04− 0 0 0 0 0 0 0 0 0 SI4+ 0 0 0 0 0 0 0 0 0 LI+ 0 00 0 0 0 0 0 0 C02 0 0 0 0 0 0 0 0 0 02 0 0 0 0 0 0 0 0 0 LI2C03 0 0 0 00 0 0 0 0 Total Flow kmol/hr 133.35 133.35 56.0071 6769.79 6769.796769.79 6769.79 77.3431 77.3431 Total Flow kg/hr 2402.34 2402.34 1008.98121960 121960 121960 121960 1393.36 1393.36 Temperature C. 150 125 12517.0233 27.0287 23 17 125 150 Pressure bar 4.75089 4.75089 4.75089 21.65526 1.48289 1.31052 4.75089 4.75089 Vapor Frac 1 0 0 0 0 0 0 00.96086 Liquid Frac 0 1 1 1 1 1 1 1 0.03914 Density kg/cum 2.43273891.302 891.302 1001.62 991.998 995.884 1001.64 891.302 2.53154

B. Experimental Data

FIG. 4 shows that high SiO₂ removal rates can be achieved for highstrength brines with only a pH adjustment, while Fe^(III) addition to aFe^(III)/Si^(IV) molar ratio=5.65 is required to achieve more than 80%Si^(IV) removal for the low strength brine. The initial pH of the brinein this experiment was 6.0-6.2. The high strength brine had acomposition as follows—Ca²⁺=425 mg/L, Cl⁻=13,100 mg/L, K⁺=630 mg/L,Mg²⁺=245 mg/L, Na⁺=7,500 mg/L, and SO₄ ²⁻=448 mg/L. The brine pH wasraised and maintained at 9.0. The brine temperature was maintained at80° C.

FIG. 5 shows that the SiO₂ precipitation process is rapid with maximumremovals achieved with a reaction time of less than 5 minutes. Theadjustment of pH combined with Fe^(III) addition and NF will achieveSiO₂ removal goals due to the efficacy of the precipitation process andrapid kinetics. In this experiment, the brine pH was increased to 9.0and the brine temperature was maintained at 80° C. Fe^(III) added to lowstrength brine at a molar ratio of Fe^(III)/Si^(IV)=5.65; No Fe^(III)was added to the high strength brine.

FIG. 6 shows nanofiltration results for the project utilizing membraneswith different molecular weight cut-offs (MWCOs). Table 2 shows thecomposition of the simulated concentrated brines that were utilized inthe nanofiltration experiments. The results indicate that high Ca²⁺ andMg²⁺ removals can be achieved utilizing nanofiltration membranes withsmaller MWCOs (˜150).

TABLE 2 Low Strength Brine High Strength Brine Component (mg/L) (mg/L)Ca 22 400-460 Cl 1,800  7,000-14,000 Li 1 20-22 Mg 13  60-230 Na 9003,400-7,000 Si 2  0-12 SO₄ 63 380-400

What is claimed is:
 1. An apparatus comprising: a) a housing comprisinga first inlet and a first outlet, wherein the housing comprises a bottomwall and an opposed top wall, wherein the bottom wall and the top wallare spaced apart relative to a vertical axis, wherein the first inletand the first outlet are spaced apart relative to a longitudinal axis,wherein the housing is in communication with a silica removal unit viathe first inlet; b) a hydrophobic membrane positioned within thehousing, wherein the hydrophobic membrane is positioned between the topwall of the housing and both the first inlet and the first outletrelative to the vertical axis; and c) a thermoelectric module positionedwithin the housing, wherein the thermoelectric module is positionedbetween the top wall and the hydrophobic membrane and spaced apart fromthe hydrophobic membrane relative to the vertical axis, c1) a conduitpositioned between the top wall and the thermoelectric module, whereinthe conduit extends between a second inlet and a second outlet spacedapart relative to the longitudinal axis, wherein the silica removal unitis in further communication with an second apparatus comprising: d) ahousing comprising a first inlet and a first outlet, wherein the housingcomprises a bottom wall and an opposed top wall, wherein the bottom walland the top wall are spaced apart relative to a vertical axis, whereinthe first inlet and the first outlet are spaced apart relative to alongitudinal axis; e) a hydrophobic membrane positioned within thehousing, wherein the hydrophobic membrane is positioned between the topwall of the housing and both the first inlet and the first outletrelative to the vertical axis; and f) a thermoelectric module positionedwithin the housing, wherein the thermoelectric module is positionedbetween the top wall and the hydrophobic membrane and spaced apart fromthe hydrophobic membrane relative to the vertical axis, f1) a conduitpositioned between the top wall and the thermoelectric module, whereinthe conduit extends between a second inlet and a second outlet spacedapart relative to the longitudinal axis.
 2. The apparatus of claim 1,wherein the housing is in communication with a mineral recovery unit viathe first outlet.
 3. The apparatus of claim 1, wherein the housing is incommunication with a polyvalent ion removal unit via the first inlet. 4.A method for generating electricity and recovering a mineral from abrine comprising the steps of: a) providing a first brine comprisingwater, silica, one or more polyvalent ions, and at least one mineralfrom a well, wherein the first brine has a temperature below about 300°C.; b) removing at least a portion of the silica from the first brine,thereby producing a second brine; c) removing at least a portion of thewater from the second brine by passing water vapor generated from thesecond brine through a hydrophobic membrane, thereby producing a thirdbrine, wherein the third brine has a higher concentration of the atleast one mineral than the second brine; d) contacting at least aportion of the water vapor that passed through the hydrophobic membranewith a thermoelectric module, thereby generating electricity; and e)recovering at least a portion of the at least one mineral from the thirdbrine, wherein the metho is performed in the apparatus of claim
 1. 5.The method of claim 4, wherein the at least one mineral compriseslithium, zinc, magnesium, or uranium, or a combination thereof.
 6. Themethod of claim 4, wherein the concentration of the at least one mineralin the first brine is less than 0.1 wt %.
 7. The method of claim 4,wherein the temperature of the first brine is from about 90° C. to about190° C.
 8. The method of claim 4, wherein the second brine has a silicaconcentration of less than 0.01 wt %.
 9. The method of claim 4, whereinthe method further comprises before step c) a step comprising removingat least a portion of the one or more polyvalent ions present in thefirst brine.
 10. The method of claim 4, wherein the concentration of theat least one mineral in the third brine is from about 0.02 wt % to about0.3 wt %.
 11. The method of claim 4, wherein the thermoelectric moduleis configured to operate with a hot side of at a temperature from about100° C. to about 180° C., and a cool side of about 10° C. to about 80°C.
 12. The method of claim 4, wherein recovering at least a portion ofthe at least one mineral from the third brine comprises extracting theat least one mineral from the third brine.
 13. A method for generatingelectricity and recovering a mineral from a brine comprising the stepsof: a) providing a first brine comprising water, silica, one or morepolyvalent ions, and at least one mineral from a well, wherein the firstbrine has a temperature below about 300° C.; b) removing at least aportion of the water from the first brine by passing water vaporgenerated from the first brine through a first hydrophobic membrane,thereby producing a fourth brine, wherein the fourth brine is at leastabout 5% more concentrated in total solids than the first brine; c)contacting at least a portion of the water vapor that passed through thefirst hydrophobic membrane with a thermoelectric module, therebygenerating electricity; d) removing at least a portion of the silica andremoving at least a portion of the one or more polyvalent ions from thefourth brine, thereby producing a fifth brine; e) removing at least aportion of the water from the fifth brine by passing water vaporgenerated from the fifth brine through a second hydrophobic membrane,thereby producing a sixth brine, wherein the sixth brine has a higherconcentration of the at least one mineral than the fifth brine; and f)recovering at least a portion of the at least one mineral from the sixthbrin, wherein the method is performed in the apparatus of claim
 1. 14.The method of claim 13, wherein the method further comprises contactingat least a portion of the water vapor that was generated from the fifthbrine and passed through the second hydrophobic membrane with athermoelectric module, thereby generating electricity.
 15. The method ofclaim 13, wherein the first brine has a temperature below about 190° C.16. The method of claim 13, wherein the second brine has a temperaturebelow 150° C. in step d).
 17. The method of claim 13, wherein the firsthydrophobic membrane is a ceramic hydrophobic membrane.
 18. The methodof claim 13, wherein the second hydrophobic membrane is a polymerichydrophobic membrane.